Sensitive visual detection of norfloxacin in water by smartphone assisted colorimetric method based on peroxidase-like active cobalt-doped Fe3O4 nanozyme.

Norfloxacin is widely used owing to its strong bactericidal effect on Gram-negative bacteria. However, the residual norfloxacin in the environment can be biomagnified via food chain and may damage the human liver and delay the bone development of minors. Present work described a reliable and sensitive smartphone colorimetric sensing system based on cobalt-doped Fe3O4 magnetic nanoparticles (Co-Fe3O4 MNPs) for the visual detection of norfloxacin. Compared with Fe3O4, Co-Fe3O4 MNPs earned more remarkably peroxidase-like activity and TMB (colorless) was rapidly oxidized to oxTMB (blue) with the presence of H2O2. Interestingly, the addition of low concentration of norfloxacin can accelerate the color reaction process of TMB, and blue deepening of the solution can be observed with the naked eye. However, after adding high concentration of norfloxacin, the activity of nanozyme was inhibited, resulting in the gradual fading of the solution. Based on this principle, a colorimetric sensor integrated with smartphone RGB mode was established. The visual sensor exhibited good linearity for norfloxacin monitoring in the range of 0.13-2.51 µmol/L and 17.5-100 µmol/L. The limit of visual detection was 0.08 µmol/L. In the actual water sample analysis, the spiked recoveries of norfloxacin were over the range of 95.7%-104.7 %. These results demonstrated that the visual sensor was a convenient and fast method for the efficient and accurate detection of norfloxacin in water, which may have broad application prospect.

Single-Atom Ce-Doped Metal Hydrides with High Phosphatase-like Activity Amplify Oxidative Stress-Induced Tumor Apoptosis.

Phosphates within tumors function as key biomolecules, playing a significant role in sustaining the viability of tumors. To disturb the homeostasis of cancer cells, regulating phosphate within the organism proves to be an effective strategy. Herein, we report single-atom Ce-doped Pt hydrides (Ce/Pt-H) with high phosphatase-like activity for phosphate hydrolysis. The resultant Ce/Pt-H exhibits a 26.90- and 6.25-fold increase in phosphatase-like activity in comparison to Ce/Pt and Pt-H, respectively. Mechanism investigations elucidate that the Ce Lewis acid site facilitates the coordination with phosphate groups, while the surface hydrides enhance the electron density of Pt for promoting catalytic ability in H2O cleavage and subsequent nucleophilic attack of hydroxyl groups. Finally, by leveraging its phosphatase-like activity, Ce/Pt-H can effectively regulate intracellular phosphates to disrupt redox homeostasis and amplify oxidative stress within cancer cells, ultimately leading to tumor apoptosis. This work provides fresh insights into noble-metal-based phosphatase mimics for inducing tumor apoptosis.

Kill Two Birds with One Stone: Dual-Metal MOF-Nanozyme-Decorated Hydrogels with ROS-Scavenging, Oxygen-Generating, and Antibacterial Abilities for Accelerating Infected Diabetic Wound Healing.

Diabetic wounds tend to develop into nonhealing wounds associated with the complex inflammatory microenvironment of uncontrollable bacterial infection, reactive oxygen species (ROS) accumulation, and chronic hypoxia. Damaged blood vessels hinder metabolic circulation, aggravating hypoxia, and ROS accumulation and further exacerbating the diabetic wound microenvironment. However, existing treatments with a single functionality have difficulty healing complicated diabetic wounds. Therefore, developing an integrative strategy to improve the hostility of the diabetic wound microenvironment is urgently needed. Herein, multifunctional genipin (GP)-crosslinked chitosan (CS)-based hydrogels decorated with the biomimetic metal-organic framework (MOF)-nanozymes and the natural antibacterial agent chlorogenic acid (CGA), which is named MOF/CGA@GP-CS (MCGC), are prepared. With catalase (CAT)-like activity, these dual-metal MOF-nanozymes are promising bioreactors for simultaneously alleviating ROS accumulation and hypoxia by converting elevated endogenous H2O2 into dissolved oxygen in diabetic wounds. In addition, the other component of natural polyphenolic CGA acts as a mild antibacterial agent, efficiently inhibiting wound infection and avoiding antibiotic resistance. Impressively, the MCGC hydrogels accelerate infected diabetic wound healing by eliminating oxidative stress, increasing oxygenation, and reversing bacterial infection in vivo. In this work, an effective strategy based on multifunctional hydrogel wound dressings is successfully developed and applied in diabetic wound management.

Colorimetric immunoassay of furazolidone metabolites based on iron-copper bimetallic organic framework nanoenzyme.

Based on the peroxidase activity of Cu-hemin metal-organic framework (Cu-hemin MOF) nanozyme, a colorimetric enzyme-linked immunosensor was developed for the detection of furazolidone (FZD). Cu-hemin MOF is a bimetallic nanozyme that exhibited a stronger catalytic effect compared with single-metal organic framework nanoenzymes. Cu-hemin-MOF catalyzes hydrogen peroxide (H2O2) to produce hydroxyl radicals (•OH), which oxidizes the chromogenic substrate 3,3',5,5'-tetramethylbenzidine (TMB) to blue oxidized TMB (oxTMB). The absorbance change is at 650 nm. The content of AOZ in animal food can be quickly and accurately determined by changes in absorbance. The linear range of the colorimetric biosensor for detecting FZD was 0.01 ~ 62.52 ng/mL, and the limit of detection was as low as 0.01 ng/mL. The recovery of spikes samples was in the range 94.2-108.0 % and reproducibility was less than 4.8%. In addition, the cross-reaction rate was less than 0.1% when detecting other metabolites except AOZ, indicating that the sensor has good applicability and specificity. This study not only provides a better understanding of the relationship between the dispersion of nanoenzymes and enzyme-like activity but also offers a general method for detecting antibiotics using the nanoenzyme colorimetric method.

Au@Pd nanozyme-mediated catalytic therapy: a novel strategy for targeting tumor microenvironment in cancer treatment.

BACKGROUND: Breast cancer, with its high morbidity and mortality rates, is a significant global health burden. Traditional treatments-surgery, chemotherapy, and radiotherapy-are widely used but come with drawbacks such as recurrence, metastasis, and significant side effects, including damage to healthy tissues. To address these limitations, new therapeutic strategies are being developed. Peroxidases (POD) can catalyze excess H2O2 in the tumor microenvironment to generate reactive oxygen species (ROS), which induce cancer cell apoptosis by disrupting redox homeostasis and modulating apoptosis-related proteins. However, natural enzymes face challenges like poor stability, high cost, and sensitivity to environmental conditions, limiting their application in breast cancer treatment. Nanozymes, nanomaterials with enzyme-like activity, offer a promising alternative by overcoming these limitations. METHODS: In this study, we successfully prepared Au@Pd nanozymes with peroxidase activity by depositing metallic Pd on Au nanoparticles (Au NPs) synthesized using a trisodium citrate reduction method and ascorbic acid reduction. The in vitro validation was conducted through a series of experiments, including ROS detection, flow cytometry, CCK-8 assay, DNA damage assessment, live/dead cell staining, Western blot (WB), and qPCR. Tumor treatment was performed via tail vein injection of the drug, followed by HE staining of the treated tissues and biochemical analysis of the blood. RESULTS: Au@Pd nanozymes can effectively accumulate at the tumor site through the EPR effect and exert peroxidase-like activity, catalyzing the excess H2O2 in the tumor microenvironment to produce ROS. This triggers apoptosis pathways and DNA damage, leading to the downregulation of the anti-apoptotic protein Bcl-2, upregulation of the pro-apoptotic protein Bax, and induction of apoptosis-related genes, demonstrating strong anti-tumor effects. CONCLUSIONS: This study developed an efficient nanozyme-mediated catalytic therapy strategy targeting the tumor microenvironment for the treatment of breast cancer cells.

Engineering Biodegradable Hollow Silica/Iron Composite Nanozymes for Breast Tumor Treatment through Activation of the "Ferroptosis Storm".

The activation of cellular ferroptosis is promising in tumor therapy. However, ferroptosis is parallelly inhibited by antiferroptotic substances, including glutathione peroxidase 4 (GPX4), dihydroorotate dehydrogenase (DHODH), and ferroptosis suppressor protein 1 (FSP1). Thus, it is highly desirable, yet challenging, to simultaneously suppress these three antiferroptotic substances for activating ferroptosis. Here, we rationally designed a hollow iron-doped SiO2-based nanozyme (FeSHS) loaded with brequinar (BQR) and lificiguat (YC-1), named FeSHS/BQR/YC-1-PEG, for tumor ferroptosis activation. FeSHS were developed through the continuous etching of SiO2 nanoparticles by iron ions, which exhibit pH/glutathione-responsive biodegradability, along with mimicking the activities of peroxidase, glutathione oxidase, and NAD(P)H oxidase. Specifically, glutathione depletion and NAD(P)H oxidation by FeSHS will suppress the expression of GPX4 and inhibit FSP1 by disrupting the NAD(P)H/FSP1/ubiquinone axis. In addition, the released BQR can suppress the expression of DHODH. Meanwhile, YC-1 is able to increase the cellular polyunsaturated fatty acids (PUFAs) by destroying the HIF-1α/lipid droplet axis. The elevation of levels of iron and PUFAs while simultaneously disrupting the GPX4/DHODH/FSP1 inhibitory pathways by our designed nanoplatform displayed high therapeutic efficacy both in vitro and in vivo. This work elucidates rationally designing smart nanoplatforms for ferroptosis activation and future tumor treatments.

A dual-mode composite nanozyme-based cascade colorimetric-fluorescence aptasensor for Salmonella Typhimurium detection.

BACKGROUND: Salmonella Typhimurium poses a serious threat to human health worldwide, necessitating the development of a rapid, sensitive, and convenient method for S. Typhimurium detection. Nanozymes are considered ideal signal report elements, which are extensively used for developing colorimetric methods. However, single-component nanozymes display low catalytic activity, and colorimetric methods are susceptible to environmental interference, reducing the sensitivity and accuracy of detection results. To address these drawbacks, this study constructed a dual-mode composite nanozyme-based cascade colorimetric-fluorescence aptasensor for S. Typhimurium detection in food. RESULTS: In this study, the composite Fe3O4@MIL-100(Fe) nanozymes were successful synthesized and demonstrated substantial peroxide-like activity, with 4.76-fold higher specificity activity (SA) than that of Fe3O4 nanozymes. Then, a glucose oxidase (GOx)-Fe3O4@MIL-100(Fe) cascade reaction was developed for colorimetric detection via an aptamer to facilitate the formation of Fe3O4@MIL-100(Fe)/S. Typhimurium/carboxylated g-C3N4 (CCN)-GOx sandwich complexes. Meanwhile, the fluorescence mode was achieved by measuring the fluorescence intensity of the sandwich complexes. In optimum conditions, the dual-mode detection limits (LOD) were 1.8 CFU/mL (colorimetric mode) and 1.2 CFU/mL (fluorescence mode), respectively, with the S. Typhimurium concentration ranging from 10 CFU/mL to 107 CFU/mL. Finally, the feasibility of the dual-mode colorimetric-fluorescence method was validated via three actual samples, yielding recovery rates of 77.32 % to91.17 % and 82.17 % to 103.7 %, respectively. SIGNIFICANCE AND NOVELTY: This study successfully develops a composite nanozyme-based cascade colorimetric and fluorescence dual-mode aptasensor for S. Typhimurium detection. It presents several distinct benefits, such as a broader linear range (10-107 CFU/mL), a lower LOD value (1.2 CFU/mL), and more accurate results. More importantly, the proposed dual-mode method displays a low LOD in colorimetric mode, demonstrating considerable potential for S. Typhimurium on-site detection in food.

V-doped MoS2 nanozymes providing reactive oxygen species and depleting glutathione for photothermally-enhanced nanocatalytic therapy.

Introduction: The tumor microenvironment and multidrug resistance of tumor cells seriously impair the activity of the nanozymes. Methods: Herein, a polyethylene glycol (PEG)-modified vanadium-doped molybdenum disulfide (V-MoS2@PEG) nanozymes were constructed to enhance anti-tumor activity through multi-enzymatic catalysis and photothermal effect with simultaneous reactive oxygen species replenishment and glutathione depletion. Results and discussion: V-MoS2@PEG nanosheets exerted peroxidase activity by causing molybdenum ion (Mo4+) to react with hydrogen peroxide to form toxic hydroxyl radicals (·OH). Meanwhile, the V-doping can deplete glutathione avoiding ·OH consumption. In addition, the high heat generated by V-MoS2@PEG nanozymes under near-infrared laser irradiation brought about a desirable local temperature gradient, which produced an enhanced catalytic effect by promoting band bending. Furthermore, the photothermally inspired polarized charge increased the permeability of the tumor cell membrane and promoted further aggregation of the nanozymes, which realized the combination of photothermal therapy with multi-enzymatic catalysis, solved the problem of multi-enzyme catalysis, and improved the anti-tumor efficiency.

Unveiling the role of heterophase nanostructure in MnO2-based colorimetric sensors for ascorbic acid detection.

Nanozymes based on manganese oxide (MnO2) are demonstrated to be promising probes in colorimetric sensing applications. In this study, the r-MnO2/ß-MnO2 heterophase nanostructure was simply prepared by a calcination process with controllable temperature. The characterization of the nanostructured material was confirmed by SEM, UV-vis spectroscopy, Raman, TGA-DSC, and XRD analysis. The r-MnO2/ß-MnO2 exhibits a remarkably good catalytic activity in the oxidation process of 3,3',5,5'-tetramethylbenzidine (TMB) compared with the r-MnO2 or Mn2O3 nanostructure owing to its heterophase junctions. The enhanced performance of the colorimetric sensor for ascorbic acid (AA) detection was investigated using the r-MnO2/ß-MnO2 heterophase nanostructure as probe. The r-MnO2/ß-MnO2 material enhanced the monitoring of AA in the wide linear range from 1 µM to 50 µM with a limit of detection of 0.84 µM. This work presents a promising and straightforward approach for the construction of MnO2-based colorimetric sensor and their practical application in plant growth monitoring.

PdMoPtCoNi High Entropy Nanoalloy with d Electron Self-Complementation-Induced Multisite Synergistic Effect for Efficient Nanozyme Catalysis.

Engineering multimetallic nanocatalysts with the entropy-mediated strategy to reduce reaction activation energy is regarded as an innovative and effective approach to facilitate efficient heterogeneous catalysis. Accordingly, conformational entropy-driven high-entropy alloys (HEAs) are emerging as a promising candidate to settle the catalytic efficiency limitations of nanozymes, attributed to their versatile active site compositions and synergistic effects. As proof of the high-entropy nanozymes (HEzymes) concept, elaborate PdMoPtCoNi HEA nanowires (NWs) with abundant active sites and tuned electronic structures, exhibiting peroxidase-mimicking activity comparable to that of natural horseradish peroxidase are reported. Density functional theory calculations demonstrate that the enhanced electron abundance of HEA NWs near the Fermi level (EF) is facilitated via the self-complementation effect among the diverse transition metal sites, thereby boosting the electron transfer efficiency at the catalytic interface through the cocktail effect. Subsequently, the HEzymes are integrated with a portable electronic device that utilizes Internet of Things-driven signal conversion and wireless transmission functions for point-of-care diagnosis to validate their applicability in digital biosensing of urinary biomarkers. The proposed HEzymes underscore significant potential in enhancing nanozymes catalysis through tunable electronic structures and synergistic effects, paving the way for reformative advancements in nano-bio analysis.

Discovery of FeP/Carbon Dots Nanozymes for Enhanced Peroxidase-Like Catalytic and Antibacterial Activity.

Iron phosphide/carbon (FeP/C) serving as electrocatalysts exhibit excellent activity in oxygen reduction reaction (ORR) process. H2O2 catalyzed by peroxidase (POD) is similar to the formation of new electron transfer channels and the optimization of adsorption of oxygen-containing intermediates or desorption of products in ORR process. However, it is still a challenge to discover FeP/C with enhanced POD-like catalytic activity in the electrocatalytic database for biocatalysis. The discovery of FeP/carbon dots (FeP/CDs) nanozymes driven by electrocatalytic activity for enhanced POD-like ability is demonstrated. FeP/CDs derived from CDs-Fe3+ chelates show enhanced POD-like catalytic and antibacterial activity. FeP/CDs exhibit enhanced POD-like activities with a specific activity of 31.1 U mg-1 that is double higher than that of FeP. The antibacterial ability of FeP/CDs nanozymes with enhanced POD-like activity is 98.1%. The antibacterial rate of FeP/CDs nanozymes (250 µg mL-1) increased by 5%, 15%, and 36% compared with FeP, Fe2O3/CDs, and Cu3P/CDs nanozymes, respectively. FeP/CDs nanozymes will attract more efforts to discover or screen transition metal phosphide/C nanozymes with enhanced POD-like catalytic activity for biocatalysis in the electrocatalytic database.

Deep convolutional neural network-based 3D fluorescence sensor array for sugar identification in serum based on the oxidase-mimicking property of CuO nanoparticles.

Developing sensor arrays capturing comprehensive fluorescence (FL) spectra from a single probe is crucial for understanding sugar structures with very high similarity in biofluids. Therefore, the analysis of highly similar sugar' structures in biofluids based on the entire FL of a single nanozyme probe needs more concern, which makes the development of novel alternative approaches highly wanted for biomedical and other applications. Herein, a well-designed deep learning model with intrinsic information of 3D FL of CuO nanoparticles (NPs)' oxidase-like activity was developed to classify and predict the concentration of a group of sugars with very similar chemical structures in different media. The findings presented that the overall accuracy of the developed model in classifying the nine selected sugars was (99-100 %), which prompted us to transfer the developed model to predict the concentration of the selected sugars at a concentration range of (1-100 µM). The transferred model also gave excellent results (R2 = 97-100 %). Therefore, the model was extended to other more complex applications, namely the identification of mixtures of sugars in serum and the detection of polysaccharides in different media such as serum and lake water. Notably, LOD for fructose was determined at 4.23 nM, marking a 120-fold decrease compared to previous studies. Our developed model was also compared with other deep learning-based models, and the results have demonstrated remarkable progress. Moreover, the identification of other possible coexisting interference substances in lake water samples was considered. This work marks a significant advancement, opening avenues for the widespread application of sensor arrays integrating nanozymes and deep learning techniques in biomedical and other diverse fields.

Designing intelligent bioorthogonal nanozymes: Recent advances of stimuli-responsive catalytic systems for biomedical applications.

Bioorthogonal nanozymes have emerged as a potent tool in biomedicine due to their unique ability to perform enzymatic reactions that do not interfere with native biochemical processes. The integration of stimuli-responsive mechanisms into these nanozymes has further expanded their potential, allowing for controlled activation and targeted delivery. As such, intelligent bioorthogonal nanozymes have received more and more attention in developing therapeutic approaches. This review provides a comprehensive overview of the recent advances in the development and application of stimuli-responsive bioorthogonal nanozymes. By summarizing the design outlines for anchoring bioorthogonal nanozymes with stimuli-responsive capability, this review seeks to offer valuable insights and guidance for the rational design of these remarkable materials. This review highlights the significant progress made in this exciting field with different types of stimuli and the various applications. Additionally, it also examines the current challenges and limitations in the design, synthesis, and application of these systems, and proposes potential solutions and research directions. This review aims to stimulate further research toward the development of more efficient and versatile stimuli-responsive bioorthogonal nanozymes for biomedical applications.

Synthesis of Mo-Pt/CeO2 Dual Single-Atom Nanozyme for Multifunctional Biochemical Detection Applications.

Elaborated structural modulation of Pt-based artificial nanozymes can efficiently improve their catalytic activity and expand their applications in clinical diagnosis and biochemical sensing. Herein, a highly efficient dual-site peroxidase mimic composed of highly dispersed Pt and Mo atoms is reported. The obtained Mo-Pt/CeO2 exhibits exceptional peroxidase-like catalytic activity, with a Vmax as high as 34.16 × 10-8 m s-1, which is 37.5 times higher than that of the single-site counterpart. Mechanism studies suggest that the Mo atoms can not only serve as adsorption and activation sites for the H2O2 substrate but also regulate the charge density of Pt centers to promote the generation ability of •OH. As a result, the synergistic effect between the dual active sites significantly improves the catalytic efficiency. Significantly, the application of the Mo-Pt/CeO2 catalyst's excellent peroxidase-like activity is extended to various biochemical detection applications, including the trace detection of glucose and cysteine, as well as the assessment of antioxidants' antioxidant capacity. This work reveals the great potential of rational design dual-site active centers for constructing high-performance artificial nanozymes.

Nanozymes targeting mitochondrial repair in disease treatment.

Mitochondria are crucial sites for biological oxidation and substance metabolism and plays a vital role in maintaining intracellular homeostasis. When mitochondria undergo oxidative damage or dysfunction, they can harm the organism, leading to various reactive oxygen species (ROS)-related diseases. Therefore, therapies targeting mitochondria are a strategy for treating multiple diseases. Many nanozymes can mimic antioxidant enzymes, which enables them to eliminate ROS to mitigate mitochondrial dysfunction. The therapeutic approaches and drugs targeting the mitochondrial electron transport chain (ETC) have emerged as effective treatments for oxidative stress-related diseases resulting from mitochondrial respiratory chain disorders. Therefore, nanozymes that can regulate homeostasis in the mitochondrial ETC have emerged as effective therapeutic agents for treating oxidative stress-related diseases. In addition, benefit from the controllability and modifiability of nanozymes, their modification with TPP, SS-31 peptide, and mitochondrial permeability membrane peptide to eliminate ROS and repair mitochondrial function. The nanozymes that specifically target mitochondria are powerful tools for the treatment of ROS-associated disorders. We discussed the design strategies pertaining to mitochondrion-targeted nanozymes to treat various diseases to develop more efficacious nanozyme tools for the treatment of ROS-related diseases in the future.

Emphasizing laccase based amperometric biosensing as an eventual panpharmacon for rapid and effective detection of phenolic compounds.

Phenols and phenolic compounds are major plant metabolites used in industries to produce pesticides, dyes, medicines, and plastics. These compounds enter water bodies, soil, and living organisms via such industrial routes. Some polyphenolic compounds like phenolic acids, flavonoids have antioxidant and organoleptic qualities, as well as preventive effects against neurodegenerative illnesses, cardiovascular disease, diabetes, and cancer. However, many of the polyphenolic compounds, such as Bisphenol A, phthalates, and dioxins also cause major environmental pollution and endocrine disruption, once the dose level becomes objectionable. The development of reliable and rapid methods for studying their dose dependency, high-impact detrimental effects, and continuous monitoring of phenol levels in humans and environmental samples is a crucial necessity of the day. Enzymatic biosensors employing phenol oxidases like tyrosinase, peroxidase and laccase, utilizing electrochemical amperometric methods are innovative methods for phenol quantification. Enzymatic biosensing, being highly sensitive and efficacious technique, is illuminated in this review article as a progressive approach for phenol quantification with special emphasis on laccase amperometric biosensors. Even more, the review article discussion is extended up to nanozymes, composites of metal organic frameworks (MOFs), and molecularly imprinted polymers (MIPs) as some emerging species for electro-chemical sensing of phenols. Applications of phenol quantification and green biosensing are also specified. A concrete summary of the innovative polyphenol detection approaches with futuristic scope indicates a triumph over some existing constraints of the phenomenological approaches providing an informative aisle to the modern researchers towards the bulk readability.

Nanozyme-Enabled Biomedical Diagnosis: Advances, Trends, and Challenges.

As nanoscale materials with the function of catalyzing substrates through enzymatic kinetics, nanozymes are regarded as potential alternatives to natural enzymes. Compared to protein-based enzymes, nanozymes exhibit attractive characteristics of low preparation cost, robust activity, flexible performance adjustment, and versatile functionalization. These advantages endow them with wide use from biochemical sensing and environmental remediation to medical theranostics. Especially in biomedical diagnosis, the feature of catalytic signal amplification provided by nanozymes makes them function as emerging labels for the detection of biomarkers and diseases, with rapid developments observed in recent years. To provide a comprehensive overview of recent progress made in this dynamic field, here an overview of biomedical diagnosis enabled by nanozymes is provided. This review first summarizes the synthesis of nanozyme materials and then discusses the main strategies applied to enhance their catalytic activity and specificity. Subsequently, representative utilization of nanozymes combined with biological elements in disease diagnosis is reviewed, including the detection of biomarkers related to metabolic, cardiovascular, nervous, and digestive diseases as well as cancers. Finally, some development trends in nanozyme-enabled biomedical diagnosis are highlighted, and corresponding challenges are also pointed out, aiming to inspire future efforts to further advance this promising field.

Emerging Nanomaterials as Versatile Nanozymes: A New Dimension in Biomedical Research.

The enzyme-mimicking nature of versatile nanomaterials proposes a new class of materials categorized as nano-enzymes, ornanozymes. They are artificial enzymes fabricated by functionalizing nanomaterials to generate active sites that can mimic enzyme-like functions. Materials extend from metals and oxides to inorganic nanoparticles possessing intrinsic enzyme-like properties. High cost, low stability, difficulty in separation, reusability, and storage issues of natural enzymes can be well addressed by nanozymes. Since 2007, more than 100 nanozymes have been reported that mimic enzymes like peroxidase, oxidase, catalase, protease, nuclease, hydrolase, superoxide dismutase, etc. In addition, several nanozymes can also exhibit multi-enzyme properties. Vast applications have been reported by exploiting the chemical, optical, and physiochemical properties offered by nanozymes. This review focuses on the reported nanozymes fabricated from a variety of materials along with their enzyme-mimicking activity involving tuning of materials such as metal nanoparticles (NPs), metal-oxide NPs, metal-organic framework (MOF), covalent organic framework (COF), and carbon-based NPs. Furthermore, diverse applications of nanozymes in biomedical research are discussed in detail.

Monodispersed Au nanoparticles decorated MoS2 nanosheets with enhanced peroxidase-like activity based electrochemical H2O2 sensing for anticancer drug evaluations.

BACKGROUND: The unique size, physical and chemical properties, and ultra-high stability of nanozymes have attracted extensive attentions in sensing, but improvement of catalytic activity of the nanozymes is still an urgent issue. Given the ultra-high simulated enzyme activity of metal nanoparticles and the advantage of multi-enzyme catalysis, an Au-decorated MoS2 nanosheets (MoS2/Au NS) integrating the double peroxidase-like (POD) activity is developed. RESULTS: By optimizing and adjusting the density of AuNPs, as well as its morphology and other parameters, a monodisperse and high-density distribution of AuNPs on MoS2 nanosheets was obtained, which can greatly improve the POD-like activity of MoS2/Au NS. Nafion solution was applied to assist the modification of MoS2/Au NS on the electrode surface so as to improved its stability. An electrochemical H2O2 detection platform was constructed by modifying MoS2/Au NS nanozyme on the SPCE using the conductive Nafion solution. And the negatively charged sulfonic acid group can eliminate negatively charged electroactive substances to improve the specificity. Then ascorbic acid was used to stimulate tumor cells to produce H2O2 as therapeutic model, an ultrasensitive chronocoulometry detection for H2O2 in cell lysate was established. The logarithmically of ΔQ and the logarithmically of H2O2 concentration showed a good linear relationship between 1 µM and 500 mM, with a LOD value of 0.3 µM. SIGNIFICANCE: The developed H2O2 sensor has excellent stability, reproducibility (RSD = 2.3 %, n = 6) and selectivity, realized the quantitative detection of H2O2 in cell lysate. Compared with commercial fluorescence detection kits for H2O2 in cell lysate, it is worth mentioning that the electrochemical H2O2 sensor developed in this study is simpler and faster, with higher sensitivity and lower cost. This provides a potential substitute for disease diagnosis and treatment evaluation based on accurate detection of H2O2.

In Situ Defect Engineering of Fe-MIL for Self-Enhanced Peroxidase-Like Activity.

Defect engineering is an effective strategy to enhance the enzyme-like activity of nanozymes. However, previous efforts have primarily focused on introducing defects via de novo synthesis and post-synthetic treatment, overlooking the dynamic evolution of defects during the catalytic process involving highly reactive oxygen species. Herein, a defect-engineered metal-organic framework (MOF) nanozyme with mixed linkers is reported. Over twofold peroxidase (POD)-like activity enhancement compared with unmodified nanozyme highlights the critical role of in situ defect formation in enhancing the catalytic performance of nanozyme. Experimental results reveal that highly active hydroxyl radical (•OH) generated in the catalytic process etches the 2,5-dihydroxyterephthalic acid ligands, contributing to electronic structure modulation of metal sites and enlarged pore sizes in the framework. The self-enhanced POD-like activity induced by in situ defect engineering promotes the generation of •OH, holding promise in colorimetric sensing for detecting dichlorvos. Utilizing smartphone photography for RGB value extraction, the resultant sensing platform achieves the detection for dichlorvos ranging from 5 to 300 ng mL-1 with a low detection limit of 2.06 ng mL-1. This pioneering work in creating in situ defects in MOFs to improve catalytic activity offers a novel perspective on traditional defect engineering.